CN110036500A - Cylindrical battery cells with the heat-shrinkable tube containing ultra-violet stabilizer - Google Patents
Cylindrical battery cells with the heat-shrinkable tube containing ultra-violet stabilizer Download PDFInfo
- Publication number
- CN110036500A CN110036500A CN201780074872.4A CN201780074872A CN110036500A CN 110036500 A CN110036500 A CN 110036500A CN 201780074872 A CN201780074872 A CN 201780074872A CN 110036500 A CN110036500 A CN 110036500A
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- CN
- China
- Prior art keywords
- heat
- battery cells
- cylindrical battery
- shrinkable tube
- cells according
- Prior art date
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- Granted
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Classifications
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
- H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2200/00—Safety devices for primary or secondary batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
A kind of cylindrical battery cells are disclosed, in the cylindrical battery cells, heat-shrinkable tube wraps up the outer surface other than electrode terminal of the battery case of the cylindrical battery cells, which includes: the substrate of polyester resin, which shrinks；The auxiliary material of nylon resin, the auxiliary material are used to improve the tensile strength and operating temperature of heat-shrinkable tube；With ultra-violet stabilizer (UV Stabilizer), the ultra-violet stabilizer is used to inhibit the chain reaction of the free radical as caused by the polymer chain break of nylon resin or polyester resin, which disconnects due to irradiating the ultraviolet light of heat-shrinkable tube.
Description
Technical field
This application claims preferential on December 26th, 2016 South Korea patent application submitted the 10-2016-0178714th
The disclosure of the South Korea patent application is integrally incorporated herein by power by reference.
The present invention relates to a kind of cylindrical battery cells with the heat-shrinkable tube containing ultra-violet stabilizer.
Background technique
As energy prices are constantly increasing and due to the pass of recent environmental pollution due to the consumption of fossil fuel
Note upgrading, the demand of environment amenable alternative energy source will necessarily be more important in future.Therefore, it is carrying out to for generating
The research of the technology of the various energy of such as nuclear energy, solar energy, wind energy and tide energy or the like, and for more efficiently using
The energy storage device of generated energy also attracts more concerns.
Particularly, with technology development and the increase in demand to mobile device, the demand to the battery as the energy is also fast
Speed increases.In addition, secondary cell is used as the power supply of electric vehicle (EV), hybrid electric vehicle (HEV) etc., and secondary electricity recently
The market in pond persistently expands to various applications, such as supplied via the accessory power supply of power grid (Grid) technology etc.As a result, right
The battery that can satisfy various demands has conducted extensive research.
In general, according to the shape of battery case, secondary cell can be divided into: including being located at cylindrical metal tank or prism
The cylindrical battery or prismatic battery of electrode assembly in shape metal can；With include be located at the pouch-shaped case made of lamination aluminium flake
The pouch-shaped battery of electrode assembly in body.Here, installation electrode assembly in the cell housing is used as and can be charged and discharged
Electric power generating element with anode, diaphragm, cathode stacked structure.Electrode assembly is broadly divided into: jelly roll electrode assembly,
Be configured with the sheet type anode for being applied active material and sheet type cathode with diaphragm be inserted in state between them into
The structure of row winding；With stacked electrode assembly, the multiple anodes and multiple cathode for being configured with predetermined size are with diaphragm
The structure that the sequence of states being inserted between them respectively stacks.
Fig. 1 is the vertical section perspective view for showing common cylindrical shaped secondary cell.
Referring to Fig.1, by the way that jelly roll (winding-type) electrode assembly 10 to be placed into cylindrical housings 13, by electrolyte
It is injected into cylindrical housings 13 and will there are the cap assemblies 14 of electrode terminal (for example, positive terminal) to be connected to circular cylindrical shell
The upper end of the opening of body 13, to manufacture column secondary battery 10.
In column secondary battery, form pipe (tube) to wrap up the outer surface of battery case, with external conductive material
Material insulate and protects the outside of battery, and the pipe as the film of electrically insulating plastic material material by being made.
However, the problem of conventional tube of column secondary battery, is, when being exposed to ultraviolet light (UV) for a long time, film by
Damage is faded, it means that its intrinsic insulation function is lost, and cannot protect the outside of battery.
Moreover, after the outer surface that pipe is attached to the battery case of column secondary battery, when be exposed to high temperature or by
When to external impact, tube capacity is easily-deformable, thus leads to defect.
Therefore, there is an urgent need to be able to solve the technology of the above problem.
Summary of the invention
Technical problem
The present invention specifically addresses the unsolved other technical problems of above problem Buddhist monk.
In order to solve the above problem it is various extensively and in-depth studies and experiment as a result, present inventor is true
Recognize, as described below, when heat-shrinkable tube includes inhibiting as produced by the polymer chain break of nylon resin and polyester resin
Free radical chain reaction ultra-violet stabilizer (UV stabilizer) when, desired effect can be obtained, complete this accordingly
Invention, the polymer chain are disconnected due to being irradiated to the ultraviolet light of heat-shrinkable tube.
Technical solution
To achieve the goals above, according to the present invention on one side, a kind of cylindrical battery cells are provided, in the cylinder
In shape battery unit, heat-shrinkable tube wraps up the outer other than electrode terminal of the cylindrical housings of the cylindrical battery cells
Surface, the heat-shrinkable tube include:
The substrate of polyester resin, the base material heated are shunk；
The auxiliary material of nylon resin, the auxiliary material improve the tensile strength and operating temperature of heat-shrinkable tube；With
Ultra-violet stabilizer (UV Stabilizer), the ultra-violet stabilizer inhibit by the nylon resin or institute
The chain reaction of free radical caused by the polymer chain break of polyester resin is stated, the polymer chain is heat-shrinked due to irradiation
The ultraviolet light of pipe and disconnect.
Therefore, because cylindrical battery cells according to the present invention include UV stabilizer, UV stabilizer inhibits due to nylon
The chain reaction of free radical caused by the polymer chain break of resin or polyester resin, wherein polymer chain is due to irradiation warm
The ultraviolet light of collapsible tube and disconnect, therefore, though heat-shrinkable tube for a long time be exposed to ultraviolet light when, the pipe will not be damaged or
It fades, it means that the intrinsic insulation function of pipe can be kept, and can protect the outside of battery.
In addition, the heat-shrinkable tube of cylindrical battery cells according to the present invention include improve heat-shrinkable tube tensile strength and
The auxiliary material of the nylon resin of operating temperature, thus, it is possible to prevent pipe deformation when being exposed to high temperature or by external impact.
Heat-shrinkable tube may also include coloring pigment, it is possible thereby to which the capacity etc. of battery unit is distinguished and shown by color
Deng, therefore be easy classification and distinguish battery.
In specific example, polyester resin can be polyethylene terephthalate (polyethylene
Terephthalate) resin.
It preferably, can include polyester resin with the amount of the 70wt% to 90wt% based on heat-shrinkable tube total weight.In detail
Ground, when including polyester resin with the amount less than 70wt%, it is difficult to obtain the required hot contraction ratio of the present invention, therefore, it is difficult to show
The function of heat-shrinkable tube.On the other hand, when including polyester resin with the amount more than 90wt%, pipe appearance when being exposed to high temperature
It is easily-deformable.
In specific example, the thickness of the heat-shrinkable tube of cylindrical battery cells can be 1 μm to 100 μm.
In specific example, ultra-violet stabilizer can be benzoic acid based compound.Preferably, benzoic acid based compound can
To be 4-HBA butyl ester (butyl-4-hydroxybenzoate).
Furthermore, it is possible to include ultra-violet stabilizer with the amount of the 0.1wt% to 5wt% of the total weight based on heat-shrinkable tube.
It preferably, include ultra-violet stabilizer with the amount of 0.5wt% to 5wt%.More specifically, including with the amount less than 0.1wt%
When ultra-violet stabilizer, it is difficult to show the function of the chain reaction of the free radical of the inhibition generation of ultra-violet stabilizer, it is thus difficult
It is cracked since ultraviolet light irradiates to prevent.On the other hand, when to be more than that the amount of 5wt% includes ultra-violet stabilizer,
It is excessively added to expensive ultra-violet stabilizer, thus compared with the stabilization effect of ultraviolet light, excessively increases manufacture
Cost.
In specific example, nylon resin can be nylon66 fiber.Nylon66 fiber has 70 degrees Celsius of higher thermal deformation temperature
Degree, 105 degrees Celsius of thermal resistance temperature, 2.9x 104kg/cm2Stretch modulus and 3.0x 104kg/cm2Bending modulus.With it
Its nylon 6, nylon 6-10 is compared with nylon 6-12, and nylon66 fiber has higher thermal resistance and higher mechanical strength.
Furthermore, it is possible to include nylon resin with the amount of the 3wt% to 10wt% of the total weight based on heat-shrinkable tube.
In addition, nylon resin can be to be blended state included in polyester resin.
It can include pigment with the amount of the 10wt% to 20wt% of the total weight based on heat-shrinkable tube in specific example.
In specific example, heat-shrinkable tube is in 61.5W/m2Intensity and 300nm to 400nm wavelength under illuminated 1000
Hour is without crackle (crack).
In specific example, heat-shrinkable tube may also include the ultraviolet light for absorbing irradiation and send out the energy of absorption as thermal energy
The ultraviolet absorbing agent penetrated.Preferably, ultraviolet absorbing agent can be benzophenone based compound, and benzophenone based compound can
To be such as dihydroxy benaophenonel (hydroxy benzophenone).
Therefore, in heat-shrinkable tube according to the present invention, ultra-violet stabilizer can prevent the crackle of film.Further, since
Heat-shrinkable tube according to the present invention further includes the ultraviolet light for absorbing the ultraviolet light of irradiation and emitting the energy of absorption as thermal energy
Absorbent, it is possible to inhibit oxidation (decomposition) of the oxygen to tube material, it is possible thereby to prevent from leading due to ultraviolet light for a long time
The deterioration of the pipe of cause.
In specific example, cylindrical battery cells can be secondary cell.The type of secondary cell is not particularly limited.
In specific example, cylindrical battery cells can be that show higher energy density, higher discharge voltage and power steady
Qualitative lithium secondary battery, such as lithium ion secondary battery, lighium polymer secondary battery or lithium ion polymer secondary cell it
Class.
In general, lithium secondary battery includes anode, cathode, diaphragm and nonaqueous electrolyte containing lithium salt.
Hereinafter, other components of lithium secondary battery will be described.
It specifically, such as can be by applying on plus plate current-collecting body comprising conductive material, adhesive and by positive-active
Cathode mix including the positive electrode active materials that material granule is constituted manufactures anode.As needed, cathode mix can be with
Include filler.
Plus plate current-collecting body is commonly manufactured as the thickness with 3 to 201 μm.Plus plate current-collecting body is not particularly limited, as long as
Do not cause any chemical change while it is with high conductivity in the battery made.For example, plus plate current-collecting body can be with
It is made of stainless steel, aluminium, nickel, titanium and surface by carbon, nickel, titanium or the processed aluminium of silver or stainless steel.Preferably, plus plate current-collecting body
It can be made of aluminum.As needed, these plus plate current-collecting bodies can also be processed to form subtle irregular structure on the surface thereof,
To increase the adhesiveness with positive electrode active materials.In addition, plus plate current-collecting body can with include film, piece, foil, net, porous structure,
Various forms including foams and non-woven body come using.
Other than positive electrode active materials particle, positive electrode active materials can be lamellar compound, such as lithium nickel oxide
(LiNiO2) or the compound as replaced one or more transition metal；By chemical formula Li1+xMn2-xO4(wherein x=0~
0.33) lithium manganese oxide or lithium manganese oxide represented by, such as LiMnO3、LiMn2O3Or LiMnO2；Lithium Cu oxide
(Li2CuO2)；Barium oxide, such as LiV3O8、LiV3O4、V2O5Or Cu2V2O7；By chemical formula LiNi1-xMxO2(wherein M=Co,
Mn, Al, Cu, Fe, Mg, B or Ga, and x=0.01~0.3) represented by the position Ni lithium nickel oxide；By chemical formula LiMn2- xMxO2(wherein M=Co, Ni, Fe, Cr, Zn or Ta, and x=0.01~0.1) or chemical formula Li2Mn3MO8(wherein M=Fe, Co,
Ni, Cu or Zn) represented by complex Li-Mn-oxide；With the Li in chemical formula partly replaced alkaline-earth metal ions
LiMn2O4；Disulfide；Or Fe2(MoO4)3, but not limited to this.
Usually to be added based on the amount of 0.1% to 30 weight % of the total weight of mixture containing a positive electrode active material
Conductive material.Any conductive material can be used without especially limiting, as long as it is with suitable electric conductivity without being made
Secondary cell in cause any chemical change.The example for the conductive material that can be used in the present invention can be led by following
Electric material is made comprising graphite, such as natural or artificial graphite；Carbon black, such as carbon black, acetylene black, Ketjen black, channel process charcoal
Black, furnace black, lampblack and thermal black；Conductive fiber, such as carbon fiber or metallic fiber；Metal powder, such as carbon fluoride powder, aluminium
Powder or nickel powder；Conductive whiskers, such as zinc oxide or potassium titanate；Conductive metal oxide, such as titanium oxide；With the derivative of polyhenylene
Object.
The adhesive for including in anode is a kind of component for increasing the viscosity of active material and conductive material and collector.It is logical
Adhesive is often added with the amount of 0.1 to 30 weight % of the total weight based on the compound containing positive electrode active materials.Adhesive
Example include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated fiber
Element, polyvinylpyrrolidone, tetrafluoroethene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonation
EPDM, styrene butadiene ribber, fluorubber and various copolymers.
It can be then dried by applying negative electrode active material on negative current collector and prepare cathode.According to need
It wants, negative electrode active material also may include the mentioned component for including in anode.
Negative current collector is commonly manufactured as the thickness with 3 to 500 μm.Negative current collector is not particularly limited, as long as
It is with suitable electric conductivity and does not cause any chemical change in the battery made.As showing for negative current collector
Example, can by copper, stainless steel, aluminium, nickel, titanium, sintering carbon and surface by carbon, nickel, titanium or the processed copper of silver or stainless steel with
And aluminium cadmium alloy is made.Similar with plus plate current-collecting body, as needed, these negative current collectors can also be processed on the surface thereof
Subtle irregular structure is formed, to increase the adhesiveness with negative electrode active material.In addition, negative current collector be formed as it is various
Form, including film, piece, foil, net, porous structure, foams and non-woven body.
In addition, the example for the negative electrode active material that can be used in the present invention includes carbon, such as hard carbon and graphitic carbon；Metal is multiple
Close oxide, such as LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、SnxMe1-xMe’yOz(Me:Mn, Fe, Pb, Ge；Me ':
Al, B, P, Si, the periodic table of elements the 1st, 2 and 3 race's elements, halogen；0≤x≤1；1≤y≤3；1≤z≤8)；Lithium metal；Lithium closes
Gold；Si system alloy；Tin system alloy；Metal oxide, such as SnO, SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、
Sb2O5、GeO、GeO2、Bi2O3、Bi2O4、Bi2O5Deng；Conducting polymer, such as polyacetylene；With Li-Co-Ni material.
Diaphragm is inserted between positive electrode and negative electrode.It is strong compared with high ion permeability and higher machinery using having as diaphragm
The insulation film of degree.Diaphragm usually has 0.01 to 10 μm of aperture and 5 to 300 μm of thickness.As diaphragm, using with resistance to
Chemically with piece or nothing made of the hydrophobic olefin polymer such as polypropylene and/or glass fibre or polyethylene
Woven fabric.When the solid electrolyte of such as polymer etc is used as electrolyte, the solid electrolyte be also used as diaphragm and
Both electrolyte.
Wrapping nonaqueous electrolyte containing lithium salt may include nonaqueous electrolyte and lithium salts.As nonaqueous electrolyte, can be used non-aqueous
Electrolyte solvent, solid electrolyte and inorganic solid electrolyte, but not limited to this.
Detailed description of the invention
Fig. 1 is the vertical section perspective view for showing common cylindrical shaped battery.
Fig. 2 is the photo for showing the experimentation of experimental example 1 of the invention.
Fig. 3 is the schematic diagram for showing the mechanism for the UV stabilizer for including in heat-shrinkable tube of the invention.
Fig. 4 is described in experimental example 2 according to the photo of the result of the heat-shrinkable tube of embodiment 1.
Fig. 5 is described in experimental example 2 according to the photo of the result of the heat-shrinkable tube of comparative example 2.
Fig. 6 is shown in experimental example 3 according to the load-deformation curve of the heat-shrinkable tube of embodiment 1 (S-S Curve)
Figure.
Fig. 7 is shown in experimental example 3 according to the load-deformation curve of the heat-shrinkable tube of comparative example 3 (S-S Curve)
Figure.
Specific embodiment
Hereinafter, the present invention will be described referring to following embodiments.The embodiment be only provided to illustrate the present invention and
It is not meant to limit the scope of the invention.
<embodiment 1>
Total weight based on composition, by the polyethylene terephthalate (polyethylene of 80g
Terephthalate), 4-HBA butyl ester (butyl-4-hydroxybenzoate), the 8g as UV stabilizer of 2g
Pigment and the nylon66 fiber of 10g mix, and melt blending prepares resin compound.Resin compound passes through quenching
Method for curing is prepared in cooling equipment, to manufacture the cylindrical heat-shrinkable tube of upper part and lower open.
<comparative example 1>
In addition to without using as the 4-HBA butyl ester (butyl-4-hydroxybenzoate) of UV stabilizer and Buddhist nun
Dragon 66 prepares other than resin combination, manufactures heat-shrinkable tube according to the same manner as in Example 1.
<comparative example 2>
In addition to being made without using the 4-HBA butyl ester (butyl-4-hydroxybenzoate) as UV stabilizer
Other than standby resin combination, heat-shrinkable tube is manufactured according to the same manner as in Example 1.
<comparative example 3>
Other than preparing resin combination without using nylon66 fiber, manufacture heat is received according to the same manner as in Example 1
The draw.
<experimental example 1>
It is of the invention that Fig. 2 shows the photos of the experimentation of experimental example 1.As shown in Fig. 2, according to embodiment 1 and ratio
Heat-shrinkable tube 110 compared with example 1 to comparative example 3 is arranged at a distance from the lamp interval 3cm of ultraviolet radiator 200, and 50
Degree Celsius temperature and 61.5W/m2Intensity under by wavelength illumination 1000 hours of 300nm to 400nm.Later, confirmation is in pipe
Surface on it is whether cracked.
[table 1]
| Cracked (zero, X) | |
| Embodiment 1 | X |
| Comparative example 1 | ○ |
| Comparative example 2 | X |
| Comparative example 3 | X |
Referring to table 1, there is crackle in no nylon and the heat-shrinkable tube according to comparative example 1 of UV stabilizer.It is another
Aspect, in the heat-shrinkable tube according to embodiment 1, comparative example 2 and comparative example 3, even if after irradiation ultraviolet light 1000 hours,
It is not cracked.That is when being added to nylon resin in the substrate of pipe of polyester resin, such as in comparative example 2, by
In the intrinsic elasticity of nylon, the crackle on heat-shrinkable tube can be prevented.In addition, when the substrate that UV stabilizer is added to pipe
When in (it being polyester resin), such as in comparative example 3, UV stabilizer inhibits the polymer chain due to nylon resin and polyester resin
The chain reaction of free radical caused by disconnecting, thus it can be prevented that crackle.
In addition, when being added to nylon resin and UV stabilizer in the substrate of pipe of polyester resin, such as in embodiment 1
In, due to the effect of synergistic effect, can further prevent forming crackle in heat-shrinkable tube.
In addition, Fig. 3 shows the schematic diagram of the mechanism for the UV stabilizer for including in heat-shrinkable tube of the invention.Referring to Fig. 3, certainly
It is reacted by base 120 with UV stabilizer 130, it is possible thereby to inhibit the chain reaction of free radical 120, free radical 120 is due to nylon tree
The polymer chain break of rouge and polyester resin and generate, wherein polymer chain is due to being irradiated to thermal contraction from UV radiator 200
The ultraviolet light of pipe 110 and disconnect.
<experimental example 2>
The heat-shrinkable tube according to embodiment 1 and the heat-shrinkable tube according to comparative example 2 are prepared, is printed with black on the surface of pipe
Writing.Heat-shrinkable tube is in 61.5W/m2Intensity and 300nm to 400nm wavelength under by UV radiator irradiate 500 hours.It
Afterwards, the color change for confirming blackness handwriting, as a result shows in figures 4 and 5.
Fig. 4 shows the color change of the heat-shrinkable tube according to embodiment 1, and Fig. 5 shows the thermal contraction according to comparative example 2
The color change of pipe.
Referring to Fig. 4 and Fig. 5, the color according to the writing on the heat-shrinkable tube of embodiment 1 is several after being irradiated with ultraviolet light
Do not change.On the other hand, grey is become from black according to the color of the writing on the heat-shrinkable tube of comparative example 2, i.e., it is dimmed
It is light.Therefore, it can be confirmed that the color of pipe does not change when heat-shrinkable tube includes UV stabilizer, but when pipe is steady not comprising UV
When determining agent, the color change of pipe is obvious.
<experimental example 3>
Three heat-shrinkable tubes according to Experimental Example 1 and three heat-shrinkable tubes according to comparative example 3 are prepared, and using omnipotent
Testing machine (Universal Test Machine) measures its tensile strength and elongation.
The sample of pipe as insulating properties sheath is placed in universal testing machine, is stretched under constant speed to measure sample
The load-deformation curve (S-S curve) of product.It is shown in FIG. 6 according to the result of the pipe of embodiment 1, according to the pipe of comparative example 3
Result be shown in FIG. 7, table 2 below shows occurrences.
[table 2]
Referring to table 2 and Fig. 6 and Fig. 7, compared with according to the heat-shrinkable tube of comparative example 3, according to the heat-shrinkable tube of embodiment 1
Tensile strength and elongation show the value significantly improved.Therefore, it can be confirmed compared with the heat-shrinkable tube for not including nylon,
Heat-shrinkable tube comprising UV stabilizer and nylon has the mechanical strength improved.It is considered that this is because according to embodiment 1
Heat-shrinkable tube includes the nylon with high-tensile and elasticity.
As it appears from the above, the substrate of heat-shrinkable tube of the invention includes nylon resin and UV stabilizer, and including nylon
Crackle is inhibited in the heat-shrinkable tube of any one in resin and UV stabilizer.Furthermore, it is possible to confirm when heat-shrinkable tube includes
When nylon resin does not still include UV stabilizer, improve its tensile strength and elongation, but when being irradiated by ultraviolet light its
Color significant change.
That is the present invention generates synergistic effect and including nylon resin and UV stabilizer together, it is possible thereby to anti-
Only due to the crackle and color change on pipe caused by ultraviolet light.
Although describing the preferred embodiment of the present invention for purposes of illustration, those skilled in the art be will become apparent from
Without departing from appended claims present invention disclosed scope and spirit in the case where, it is various change, increase and replacement be can
Can.
Industrial applicibility
As described above, the heat-shrinkable tube of cylindrical battery cells according to the present invention includes UV stabilizer, UV stabilizer suppression
The chain reaction of the free radical as caused by the polymer chain break of nylon resin or polyester resin is made, wherein polymer chain
It is disconnected due to irradiating the ultraviolet light of heat-shrinkable tube, even if when heat-shrinkable tube is exposed to ultraviolet light for a long time, the pipe
It is not damaged or fades, it means that intrinsic insulation function can be kept, and can protect the outside of battery.
In addition, the heat-shrinkable tube of cylindrical battery cells according to the present invention include improve heat-shrinkable tube tensile strength and
The auxiliary material of the nylon resin of operating temperature, thus, it is possible to prevent pipe deformation when being exposed to high temperature or external impact.
Claims (15)
1. a kind of cylindrical battery cells, in the cylindrical battery cells, heat-shrinkable tube wraps up the cylindrical battery list
The outer surface other than electrode terminal of the cylindrical housings of member, the heat-shrinkable tube include:
The substrate of polyester resin, the base material heated are shunk；
The auxiliary material of nylon resin, the auxiliary material improve the tensile strength and operating temperature of the heat-shrinkable tube；With
Ultra-violet stabilizer (UV Stabilizer), the ultra-violet stabilizer inhibit due to the nylon resin or described poly-
The chain reaction of free radical caused by the polymer chain break of ester resin, the polymer chain is due to irradiating the thermal contraction
The ultraviolet light of pipe and disconnect.
2. cylindrical battery cells according to claim 1, wherein the heat-shrinkable tube further includes coloring pigment.
3. cylindrical battery cells according to claim 1, wherein the polyester resin is polyethylene terephthalate
Ester (polyethylene terephthalate) resin.
4. cylindrical battery cells according to claim 3, wherein with the total weight based on the heat-shrinkable tube
The amount of 70wt% to 90wt% includes the polyester resin.
5. cylindrical battery cells according to claim 1, wherein the heat-shrinkable tube of the cylindrical battery cells
With a thickness of 1 μm to 100 μm.
6. cylindrical battery cells according to claim 1, wherein the UV stabilizer is benzoic acid based compound.
7. cylindrical battery cells according to claim 6, wherein the benzoic acid based compound is 4-HBA
Butyl ester (butyl-4-hydroxybenzoate).
8. cylindrical battery cells according to claim 1, wherein with the total weight based on the heat-shrinkable tube
The amount of 0.1wt% to 5wt% includes the ultra-violet stabilizer.
9. cylindrical battery cells according to claim 1, wherein the nylon resin is nylon66 fiber.
10. cylindrical battery cells according to claim 9, wherein with the total weight based on the heat-shrinkable tube
The amount of 3wt% to 10wt% includes the nylon resin.
11. cylindrical battery cells according to claim 2, wherein with the total weight based on the heat-shrinkable tube
The amount of 10wt% to 20wt% includes the pigment.
12. cylindrical battery cells according to claim 1, wherein the heat-shrinkable tube is in 61.5W/m2Intensity and
Under the wavelength of 300nm to 400nm illuminated 1000 hours without crackle (crack).
13. cylindrical battery cells according to claim 1, wherein the nylon resin is to be blended state included in described
In polyester resin.
14. cylindrical battery cells according to claim 1, wherein the heat-shrinkable tube further includes the ultraviolet of absorption irradiation
Line and the ultraviolet absorbing agent for emitting the energy of absorption as thermal energy.
15. cylindrical battery cells according to claim 14, wherein the ultraviolet absorbing agent is benzophenone series
Close object.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20160178714 | 2016-12-26 | ||
| KR10-2016-0178714 | 2016-12-26 | ||
| PCT/KR2017/015431 WO2018124674A2 (en) | 2016-12-26 | 2017-12-26 | Cylindrical battery cell having heat-shrinkable tube comprising ultraviolet stabilizer |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3528303A4 (en) | 2019-12-04 |
| CN110036500B (en) | 2022-03-11 |
| US20190280252A1 (en) | 2019-09-12 |
| JP2019535100A (en) | 2019-12-05 |
| EP3528303A2 (en) | 2019-08-21 |
| US11367911B2 (en) | 2022-06-21 |
| JP6870814B2 (en) | 2021-05-12 |
| KR20180075421A (en) | 2018-07-04 |
| KR102178899B1 (en) | 2020-11-13 |
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